EP1529798A1 - Film thermoscellable et pelable en polyester à adhésivité améliorée, procédé pour sa préparation et son usage - Google Patents

Film thermoscellable et pelable en polyester à adhésivité améliorée, procédé pour sa préparation et son usage Download PDF

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Publication number
EP1529798A1
EP1529798A1 EP20040025893 EP04025893A EP1529798A1 EP 1529798 A1 EP1529798 A1 EP 1529798A1 EP 20040025893 EP20040025893 EP 20040025893 EP 04025893 A EP04025893 A EP 04025893A EP 1529798 A1 EP1529798 A1 EP 1529798A1
Authority
EP
European Patent Office
Prior art keywords
polyester
film
mol
film according
polyester film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20040025893
Other languages
German (de)
English (en)
Inventor
Herbert Dr. Professor Pfeiffer
Bart Dr. Janssens
Matthias Dr. Konrad
Andreas Stopp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Polyester Film GmbH
Original Assignee
Mitsubishi Polyester Film GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Polyester Film GmbH filed Critical Mitsubishi Polyester Film GmbH
Publication of EP1529798A1 publication Critical patent/EP1529798A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable
    • Y10T428/2817—Heat sealable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable
    • Y10T428/2817—Heat sealable
    • Y10T428/2826—Synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • the invention relates to a biaxially oriented polyester film coated on at least one side, the z. B. as a lidding film for containers (meal trays, yogurt cups, etc.) can be used.
  • the polyester film consists of a base layer (B) and at least one cover layer (A) applied to this base layer (B).
  • the Cover layer (A) is heat-sealable and is characterized for. B. by a light to solid Peelability to APET and CPET off.
  • the film according to the invention has at least a surface that has good adhesion to other polymer or metal layers or Has printing inks.
  • the invention further relates to a process for the preparation of Foil and its use.
  • Ready meals which are enjoying increased growth rates in Europe, will be following their own Production in trays filled (see Figure 1).
  • On the edge of the Menu tray is heat sealed a foil that closes the packaging and the Ready meal protects against external influences.
  • Menu tray CPET, aluminum, PET or PET film coated carton or APET / CPET trays.
  • Menu shells from APET / CPET consist of a CPET layer on the outside and an APET layer on the inside, ie towards the ready menu.
  • the thick, crystalline CPET layer provides the stability of the shell, even at the comparatively high temperatures in the oven.
  • the amorphous PET substantially improves the adhesion of the film to the menu tray.
  • Lid film PET is usually used here, which remains dimensionally stable and strong enough even at 220 ° C. Materials such as PP or PE are eliminated because of their low melting points.
  • the requirements for the cover film are best met by biaxially oriented polyester films.
  • the polyester film When preparing the ready meal in the oven, the polyester film is about to Heating or shortly after heating, peeled off the tray by hand. In doing so, the polyester film must not be inserted, retracted or torn off. The removal of the film from the menu shell, without the film on, duroder is called “peels" in the food industry. For this Therefore, the polyester film must not only be heat-sealable, but in particular also be peelable. For a given material and given total thickness of Film is the peelability of the film mainly by the properties of the surface layer the film sealed to the tray.
  • the peelability of films can be laboratory relatively easy with a stress-strain tester (eg, Zwick, DE) (see Figure 2).
  • a stress-strain tester eg, Zwick, DE
  • For this test will be from the polyester film and from the menu tray two 15 mm wide and about 50 mm long Stripes cut out and sealed against each other. The sealed strips will be - As shown in Figure 2 - clamped in the clips of the tester. The angle" between the film clamped in the upper clip and the menu tray strip is 180 °.
  • the tethers of the tester are moving at a speed of 200 mm / min apart, the film in the best case of the Menu shell is completely peeled off (peeled). (See, eg, ASTM-B 3330).
  • the pulling force increases rapidly up to a maximum during the drawing process (see Figure 3a) and then falls directly back to zero.
  • the Maximum force tears the film in or before delaminating from the menu tray, which immediately returns the force to zero.
  • the film is not in this case peelable as it is destroyed.
  • the behavior of the film can be more of a kind Describe "weldable" with the menu shell.
  • the destruction of the Film when peeling off the menu tray is undesirable, because it makes the clean and easy opening of the packaging (easy opening) without tools such as scissors or Knife is difficult.
  • a peelable film is obtained when the tensile or peel force is up to a certain value (or up to a certain plateau) increases and then about the distance over which the two strips are sealed together, roughly remains constant (see Figure 3b). In this case, the film does not break, but can be peel off as desired from the menu shell with little effort (engl. exfoliate).
  • the height of the peel force is used primarily by those in the topcoat (A) Polymers determined (see Figure 4, Polymer 1 and Polymer 2).
  • Next to it is the height of the Peelkraft particular depending on the applied heat sealing temperature.
  • the Peelkraft usually increases with the heat sealing temperature. With increasing In this case, the heat-sealing temperature increases the risk that the sealing layer will increase its peelability loses. Ie. a film which, when using a low heat sealing temperature peelable, loses this property when a sufficiently high heat sealing temperature is applied. This behavior is especially to be expected for polymers that show the characteristic shown in Figure 4 for polymer 1. This tends to Generally accepted but for the application rather unfavorable behavior at the Design of the sealing layer are taken into account.
  • the foil must be in one sufficiently large temperature range can be heat sealed without doing so the desired peelability is lost (see Polymer 2 in Figure 4).
  • This temperature range is generally 150 to 220 ° C, preferably 150 to 200 ° C and more preferably 150 to 190 ° C.
  • the heat sealable and peelable layer is known in the art Usually by means of so-called off-line methods (ie in an additional, the film production downstream process step) applied to the polyester film.
  • off-line methods ie in an additional, the film production downstream process step
  • the polyester film thus produced is then in a further processing step in a coating plant "off-line” with a heat-sealable and coated peelable layer.
  • the heat-sealable and peelable polymer dissolved in an organic solvent.
  • the finished solution is then on a suitable application process (knife pourer, anilox roller, nozzle) on applied the foil.
  • a suitable application process quenife pourer, anilox roller, nozzle
  • the solvent evaporateates and the peelable polymer remains as a solid layer on the film back.
  • the solvent may never be complete be removed from the coating during drying, in particular because of the Drying process can not be arbitrarily long. Remaining in the coating Traces of the solvent then migrate over the film on the tray in the dishes, where they distort the taste or even the consumer can harm your health.
  • EP-A-0 379 190 discloses a biaxially oriented multilayer polyester film comprising a carrier layer of polyester and at least one sealing layer described from a polyester composition.
  • the polyester film can under Application of coextrusion technology, in-line coating, in-line Lamination or using suitable combinations of said technologies getting produced.
  • In-line coating polymers are the Sealant layer in the form of a dispersion or solution on the carrier layer applied.
  • the polymers become the sealant layer in the form of extruded melt on the carrier layer, for. B. between the two stretching steps, applied.
  • the sealant layer may contain aliphatic and aromatic dicarboxylic acids as well as aliphatic diols.
  • the polymer for the sealant layer contains two different polyesters A and B, of which at least one (polyester B) contains aliphatic dicarboxylic acids and / or aliphatic diols.
  • the sealing energy measured between two opposing, interconnected sealing film layers is greater than 400 g force cm / 15 mm (greater than 4 N cm / 15 mm), the sealant film layer being inorganic and / or organic may contain fine particles which are not soluble in the polyester and wherein the fine particles are present in an amount of from 0.1 to 5% by weight, based on the total weight of the sealing film layer.
  • the film is distinguished by good peel properties (with a plateau character in the peel diagram above) against itself (ie sealing layer against sealing layer), there is no indication of the peel behavior against the APET, CPET and APET / CPET menu shells.
  • the film according to this invention is in need of improvement in its manufacturing and processability.
  • WO-A-96/19333 describes a process for producing peelable films in which the heat-sealable, peelable layer is applied in-line to the polyester film.
  • the process uses comparatively small amounts of organic solvents.
  • the heat-sealable, peelable layer contains a copolyester containing a) 40 to 90 mol% of an aromatic dicarboxylic acid, b) 10 to 60 mol% of an aliphatic dicarboxylic acid, c) 0.1 to 10 mol% of a dicarboxylic acid containing a free acid group or a salt thereof, d) 40 to 90 mol% of a glycol containing 2 to 12 carbon atoms and e) 10 to 60 mol% of a polyalkyldiol.
  • the coating is applied to the film from an aqueous dispersion or solution containing up to 10% by weight of organic solvent.
  • the process is limited in the useful polymers and the attainable layer thicknesses for the heat-sealable, peelable layer.
  • the maximum achievable layer thickness is given as 0.5 ⁇ m.
  • the maximum seal seam strength is low, it is 500 to 600 g / 25 mm 2 , or [(500 to 600) / 170] N / 15 mm film width.
  • WO 02/059186 A1 describes a process for producing peelable films, in which the heat-sealable, peelable layer in-line on the polyester film is applied.
  • the so-called melt coating is used, preferably the longitudinally stretched film with the heat-sealable, peelable polymer is coated.
  • the heat-sealable polymer contains polyester Based on aromatic and aliphatic acids, as well as on the basis of aliphatic Diols.
  • the copolymers disclosed in the examples have glass transition temperatures from below -10 ° C; such copolyesters are too soft, which is why they are not in the usual Orient the roll stretching process (gluing on the rolls).
  • the known properties exhibiting polyester film should not deteriorate.
  • these include, for example, the good mechanical (the modulus of elasticity of the biaxially stretched films should be greater than 3500 N / mm 2 , preferably greater than 3800 N / mm 2 and more preferably greater than 4200 N / mm 2 in both orientation directions) and the thermal Properties (the shrinkage of the biaxially stretched films should not be greater than 3%, preferably not greater than 2.8% and particularly preferably not greater than 2.5% in both orientation directions), the winding behavior and the processability of the film, in particular in the case of Printing, laminating or coating the film with metallic or ceramic materials.
  • the polymer of the sealant layer generally has a much lower melting point as the polymer of the base layer.
  • the melting point of the heat sealable layer generally less than 230 °, in the present case preferably less than 210 ° C, and more preferably less than 190 ° C.
  • the composite made of heat-sealable film and substrate is when removing the film of the Substrate in the seam between the heat seal layer and the substrate surface (see also Ahlhaus, O.E .: packaging with plastics, Carl Hanser Verlag, p. 1997, ISBN 3-446-17711-6).
  • the layer thickness of the cover layer (A) d A is preferably 1.0 to 7.0 ⁇ m (measured on the biaxially oriented polyester film).
  • the material of the cover layer (A) or the cover layer film (A) consists predominantly made of a polyester.
  • the polyester is made up of units derived from aromatic and aliphatic dicarboxylic acids are derived. On the aromatic dicarboxylic acids decreasing units are preferred in the polyester in an amount of From 12 to 89 mol%, in particular from 30 to 84 mol%, particularly preferably from 40 to 82 mol%, contain.
  • the units derived from the aliphatic dicarboxylic acids are in the polyester in an amount of preferably 11 to 88 mol%, especially 16 to 70 Mole%, more preferably 18 to 60 mole%. where the mol% information always complement each other to 100%.
  • the corresponding diol units result always always 100 mol%.
  • Preferred aliphatic dicarboxylic acids are succinic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, glutaric acid and adipic acid. Especially preferred are azelaic acid, sebacic acid and adipic acid.
  • Preferred aromatic dicarboxylic acids are terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, in particular terephthalic acid and isophthalic acid.
  • Preferred diols are ethylene glycol, butylene glycol and neopentyl glycol.
  • the material of the outer layer (A) up to 10 wt .-% of other Additives, auxiliaries and / or other in polyester film technology usually used additives.
  • the material of the cover layer (A) contains from 2 to 30% by weight, preferably from 5 to 25% by weight, and more preferably 7 to 20 wt .-% of a polymer which is incompatible with polyester (anti-PET polymer).
  • the main polyester of the outer layer (A) of two Separate polyesters I and II, the (the) extruder (s) for the Formation of this layer (film) are supplied as a mixture.
  • the heat sealable and peelable topcoat (A) has over CPET or the APET side of APET / CPET menu pans a maximum sealing temperature of generally 220 C, preferably 200 ° C and particularly preferably 190 ° C, wherein in the entire seal area one towards CPET or the APET side of APET / CPET bowls peelable film is obtained. Ie. with this slide will obtained in the 180 ° tensile test according to Figure 2, a curve according to Figure 3b.
  • Menu trays are synonymous with materials in general.
  • the film of the present invention has a base layer (B) and at least a cover layer (A) according to the invention.
  • the film is two-layered built up.
  • the film is three or more than three-layered.
  • it then consists of the base layer (B), the inventive Cover layer (A) and a cover layer (C) opposite the cover layer (A); Film structure A-B-C.
  • the film contains a Intermediate layer (D) between the base layer (B) and the cover layer (A) or (C).
  • the base layer of the film preferably consists of at least 80% by weight of thermoplastic Polyester, based on the weight of the base layer (B). Suitable for that are z.
  • ethylene-containing polyesters which, based on the Dicarboxylatein surge - from at least 90 mol%, more preferably at least 95 mole%, terephthalate or 2,6-naphthalate units.
  • the remaining monomer units are derived from other dicarboxylic acids or diols.
  • copolymers or mixtures may also be used for the base layer (B) or blends of said homopolymers and / or copolymers.
  • at the indication of the amounts for the dicarboxylic acids forms the total amount of all Dicarboxylic acids 100 mol%. Similarly, the total amount of all diols also makes 100 Mol%.
  • Suitable other aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalenedicarboxylic acids (for example naphthalene-1,4- or 1,6-dicarboxylic acid), biphenyl-x, x'-dicarboxylic acids (in particular biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x '-dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'-dicarboxylic acids.
  • cycloaliphatic dicarboxylic acids mention may be made of cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid).
  • aliphatic dicarboxylic acids the (C 3 -C 19 ) alkanedioic acids are particularly suitable, it being possible for the alkane part to be straight-chain or branched.
  • Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n is an integer from 3 to 6 (in particular propane-1,3-diol, butane-1,4 -diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols having up to 6 carbon atoms, cycloaliphatic, optionally heteroatom-containing diols having one or more rings.
  • n is an integer from 3 to 6 (in particular propane-1,3-diol, butane-1,4 -diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols having up to 6 carbon atoms, cycloaliphatic, optionally heteroatom-containing
  • cyclohexanediols in particular cyclohexane-1,4-diol.
  • Suitable other aromatic diols correspond for example to the formula HO-C 6 H 4 -XC 6 H 4 -OH, where X is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O -, -S- or -SO 2 - stands.
  • bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
  • a polyester copolymer is present in the base layer (B) Based on terephthalate and small amounts (preferably ⁇ 5 mol%) of isophthalic acid or based on terephthalate and small amounts (preferably ⁇ 5 mol%) Naphthalene-2,6-dicarboxylic acid is used.
  • the base layer (B) then essentially contains a polyester copolymer consisting predominantly of Terephthalic acid and isophthalic acid units and / or terephthalic acid and Naphthalene-2,6-dicarboxylic acid units and composed of ethylene glycol units is.
  • the most preferred copolyesters have the desired properties of the film are those made of terephthalate and isophthalate units and composed of ethylene glycol units.
  • the preparation of the polyester can z. B. carried out according to the transesterification process. It is based on dicarboxylic acid esters and diols, which with the usual transesterification catalysts, such as zinc, calcium, lithium and manganese salts reacted become. The intermediates are then in the presence of commonly used polycondensation catalysts, such as antimony trioxide, titanium oxides or esters as well Germanium compounds, polycondensed. The manufacture may as well after the direct esterification process in the presence of polycondensation catalysts respectively. It starts directly from the dicarboxylic acids and diols.
  • the film according to the present invention has at least two layers. She then consists of the base layer (B) and applied to this by coextrusion sealable and peelable outer layer film (A) according to the invention.
  • the sealable and preferably by coextrusion on the base layer (B) applied peelable topcoat film (A) is predominantly, d. H. preferably at least 60 % By weight of polyesters.
  • the heat-sealable and peelable outer layer film (A) contains Polyesters based on aromatic and aliphatic acids and preferably aliphatic Diols.
  • polyesters in the preferred embodiment, copolyesters or Blends of homo- and copolyesters or blends of various copolyesters understood, based on aromatic and aliphatic dicarboxylic acids and aliphatic diols are constructed.
  • aromatic dicarboxylic acids which can be used according to the invention are Terephthalic acid, isophthalic acid, phthalic acid and 2,6 naphthalenedicarboxylic acid.
  • aliphatic dicarboxylic acids which can be used according to the invention are Succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, Azelaic acid and sebacic acid.
  • Examples of the aliphatic diols which can be used according to the invention are ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, Diethylene glycol, triethylene glycol and 1,4-cyclohexanedimethanol.
  • the polyester for the outer layer (A) is preferably made of two polyesters I and II produced.
  • the proportion of the polyester I, the one or more aromatic dicarboxylates and one or more aliphatic alkylenes, in the topcoat (A) is preferably 0 to 50 wt .-%.
  • the Proportion of the polyester I 5 to 45 wt .-% and in the particularly preferred embodiment it is 10 to 40 wt .-%.
  • the polyester I consists of a Mixture comprising a copolyester composed of terephthalate, isophthalate and of ethylene units, and an aromatic polyester homopolymer, e.g. B. a Polybutylene terephthalate, contains.
  • the proportion of polyester II in the Cover layer (A) preferably 50 to 100 wt .-%.
  • the proportion of polyester II is 55 to 95 wt .-% and in the most preferred Embodiment, it is 60 to 90 wt .-%.
  • the polyester II consists of a copolymer of aliphatic and aromatic acid components in which the aliphatic acid components preferably 20 to 90 mol%, in particular 30 to 70 mol% and particularly preferably 35 to 60 mol%, based on the total amount of acid of the polyester II.
  • the aliphatic acid components preferably 20 to 90 mol%, in particular 30 to 70 mol% and particularly preferably 35 to 60 mol%, based on the total amount of acid of the polyester II.
  • Dicarboxylatanteil derived from aromatic acids, preferred of terephthalic acid and / or isophthalic acid and on the glycolic side of aliphatic or cycloaliphatic or aromatic diols, as already described above have been described in detail with respect to the base layer.
  • any remaining parts are derived from other aromatic dicarboxylic acids and other aliphatic diols as previously described for the base layer (B) or hydroxycarboxylic acids such as hydroxybenzoic acid etc.
  • the outer layer (A) preferably contains a mixture of the polyesters I and II.
  • a mixture has the following advantages:
  • the mixture of the two polyesters I and II is easier to process (to extrude) as seen from the respective glass transition temperatures (T g ).
  • T g glass transition temperatures
  • the mixture of a high T g polymer (polyester I) and a low T g polymer (polyester II) is less susceptible to sticking in the coextruder than a single polymer having a correspondingly mixed T g .
  • the polymer production is simpler, because one usually does not have any amount of metering stations for the starting materials available.
  • the mixture practically the desired peel properties can be set more individually than when using a single polyester.
  • the addition of particles is easier with polyester I than polyester II.
  • the glass transition temperature of polyester I is more than 50 ° C.
  • the glass transition temperature of polyester I is more than 55 ° C and more preferably more than 60 ° C. Is the glass transition temperature of polyester I less than 50 ° C, the film may not be prepared process safe become.
  • the sticking tendency of the film (A) z. B. against the metallic walls of the Extruders can be so large that calculated with blockages in the extruder must become.
  • the glass transition temperature of polyester II is less than 20 ° C.
  • the glass transition temperature is less than 15 ° C and more preferably less than 10 ° C. Is the glass transition temperature of polyester II greater than 20 ° C, so the film tends to peel off the menu shell increasingly Tearing or tearing, which is undesirable.
  • the heat-sealable and peelable topcoat (A) a polyester incompatible polymer (anti-PET polymer).
  • the proportion of the polyester-incompatible polymer (anti-PET polymer) is then preferably 2 to 30 wt .-%, based on the mass of the outer layer (A).
  • the proportion of the polymer is from 5 to 25% by weight. and in the most preferred embodiment, it is 7 to 20% by weight, likewise based on the mass of the outer layer (A).
  • Suitable incompatible polymers are polymers Base of ethylene (eg LLDPE, HDPE), propylene (PP), cycloolefins (CO), amides (PA) or styrene (PS).
  • PP propylene
  • PP propylene
  • CO cycloolefins
  • PA amides
  • PS styrene
  • polyester incompatible Polymer used a copolymer.
  • Such cycloolefin copolymers are for example in EP-A-1 068 949 or in JP 05-009319 described herein incorporated by reference.
  • cycloolefin copolymers particular preference is given to those which polymerized units of norbornene-based polycyclic olefins, especially preferably norbornene or tetracyclododecene.
  • Particularly preferred Cycloolefin copolymers (COC) the polymerized units of acyclic olefins, in particular Ethylene, included.
  • COC Cycloolefin copolymers
  • norbornene / ethylene and Tetracyclododecene / ethylene copolymers containing from 5 to 80% by weight of ethylene units, preferably 10 to 60 wt .-% ethylene units (based on the mass of the copolymer).
  • the cycloolefin polymers generally have glass transition temperatures between -20 and 400 ° C.
  • such cycloolefin copolymers are particularly suitable, a glass transition temperature of less than 160 ° C, preferably less than 120 ° C and more preferably less than 80 ° C.
  • the glass transition temperature Preferably should the glass transition temperature be above 50 ° C, preferably above 55 ° C, especially above 60 ° C.
  • the viscosity number (Decalin, 135 ° C, DIN 53 728) is suitably between 0.1 and 200 ml / g, preferably between 50 and 150 ml / g.
  • Films containing a COC with a glass transition temperature of smaller than 80 ° C are distinguished from those containing a COC with a Glass transition temperature greater than 80 ° C contained, by improved optical Properties, in particular by a lower turbidity.
  • Cycloolefincopolymere happens z. B. by a heterogeneous or homogeneous catalysis with organometallic compounds and is in one Variety of documents described. Suitable catalyst systems based on Mixed catalysts of titanium or vanadium compounds in combination with aluminum organyls, are described in DD 109 224, DD 237 070 and EP-A-0 156 464.
  • EP-A-0 283 164, EP-A-0 407 870, EP-A-0 485 893 and EP-A-0 503 422 the preparation of cycloolefin copolymers (COC) with catalysts based on soluble metallocene complexes.
  • COC cycloolefin copolymers
  • Cycloolefin copolymers prepared with catalysts, which are based on soluble metallocene complexes, is particularly preferred resorted.
  • Such COC are commercially available; z. B. Topas® (Ticona, Frankfurt).
  • the processability of the film but in particular also to improve the peel behavior of the film of the It is an advantage of the tray, the heat sealable and peelable topcoat (A) on to modify.
  • At least the outer layer (A) particles in one certain size, concentration and distribution includes.
  • mixtures of two and several different Particle systems or mixtures of particle systems in the same chemical composition, but different particle size of the topcoat (A) are added.
  • Common particles are inorganic ones and / or organic particles, for example calcium carbonate, amorphous silica, Talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, Lithium phosphate, calcium phosphate, magnesium phosphate, alumina, lithium fluoride, Calcium, barium, zinc or manganese salts of the dicarboxylic acids used, Carbon black, titanium dioxide, kaolin or cross-linked polystyrene or acrylate particles.
  • the particles can the layer in the respective advantageous concentrations, eg. B. as glycolic Dispersion during polycondensation or via masterbatches during extrusion, be added.
  • Preferred particles according to the invention are synthetically produced, amorphous SiO 2 particles in colloidal form. These particles are perfectly integrated into the polymer matrix and produce only a few vacuoles (cavities). Vacuoles are formed on the particles in the biaxial orientation, generally causing turbidity, and are therefore undesirable for the present invention.
  • SiO 2 particles also called silica gel
  • first sulfuric acid and sodium silicate are mixed together under controlled conditions to form hydrosol. This eventually forms into a hard, transparent mass known as a hydrogel.
  • the hydrogel can be dried and processed further. By controlling the wash water pH and the drying conditions, the important physical parameters such.
  • pore size and the size of the surface of the resulting silica gel can be varied.
  • the desired particle size (eg the d 50 value) and the desired particle size distribution (eg the SPAN98) are obtained by suitable grinding of the silica gel (eg mechanically or hydromechanically). Such particles can, for. B. on the companies Grace, Fuji, Degussa or Ineos.
  • particles having an average particle diameter d 50 of from 2.0 to 8 ⁇ m, preferably from 2.5 to 7 ⁇ m and particularly preferably from 3.0 to 6 ⁇ m When using particles with a diameter that is below 2.0 microns, a positive influence of the particles on the peel behavior of the film from the meal tray may not be given. In this case, the film tends once again tearing or tearing when peeled off the menu tray, which is of course undesirable. Particles larger than 8 ⁇ m in diameter usually cause filter problems.
  • the diameter d 50 of the particles is greater than the thickness of this layer. It has proved to be favorable to choose a diameter / layer thickness ratio of preferably at least 1.1, in particular at least 1.3 and particularly preferably at least 1.5. In these cases, a particularly positive influence of the particles on the peel behavior of the film is given by the menu shell.
  • the concentration is preferably the particles 2.5 to 10.0 wt .-% and particularly preferably 4.0 to 10.0 wt .-%.
  • the roughness of the heat-sealable and peelable outer layer (A) so that its R a value is preferably greater than 60 nm.
  • the roughness Ra is larger than 80 nm, and particularly preferably it is greater than 100 nm; the upper limit of the roughness should not exceed 400 nm, preferably 350 nm, in particular 300 nm. This can be controlled by the choice of particle / diameter, its concentration and the variation of the layer thickness.
  • the sealable and peelable film has in particular in a three-layer film with ABC structure proved to be useful, the amount of particles lower in the base layer (B) than in the outer layer (A).
  • the Amount of particles between 0 and 2.0 wt .-% are, preferably between 0 and 1.5 wt .-%, in particular between 0 and 1.0 wt .-%.
  • it turned out to be incorporated into the base layer only particles, as they over the native reclaim (recycled material) into the film.
  • the optical properties of Film, especially the haze of the film, are then particularly good.
  • At least one film surface is treated so that the contact angle in water, preferably ⁇ 64 °, in particular ⁇ 62 °, particularly preferably ⁇ 60 °.
  • the film on the non-sealable surface with a coated functional coating so that the coating on the finished film has a thickness of preferably 5 to 2000 nm, preferably 20 to 500, in particular 30 to 200 nm.
  • the coating is preferably applied in-line, d. H. during the Folienherstellreaes, advantageously before the transverse extent.
  • Coatings are preferred as solutions, suspensions or dispersions applied, particularly preferably as an aqueous solution, suspension or dispersion.
  • the coatings mentioned give the film surface an additional function; For example, the film is thereby sealable, printable, metallizable, sterilizable, antistatic or they improve z. B. the aroma barrier or allow adhesion to materials that would otherwise not adhere to the film surface.
  • fabrics / compositions imparting additional functionality are: acrylates such as described in WO94 / 13476, ethylvinyl alcohols, PVDC, water glass (Na 2 SiO 4 ), hydrophilic polyester (5-Na-sulfoisophthalic acid containing PET / IPA polyester, as described for example.
  • polyvinyl acetates as for example, polyurethanes, alkali metal or alkaline earth metal are described in W094 / 13481, of C 10 C 18 fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid or esters thereof.
  • the substances / compositions mentioned are z. B. as a dilute solution, Emulsion or dispersion preferably as aqueous solution, emulsion or dispersion applied to one or both surfaces of the film and then the solvent volatilized. If the coatings are applied in-line before the transverse stretching, Usually, the temperature treatment in the transverse extension is sufficient to the Volatilize the solvent and dry the coating.
  • the dried ones Coatings then have layer thicknesses of 5 to 2000 nm, preferably 20 to 500 nm, in particular 30 to 200 nm.
  • a copolyester coating is used to achieve better adhesion.
  • the preferred coating copolyesters are obtained by polycondensation of a) isophthalic acid, b) an aliphatic dicarboxylic acid having the formula HOOC (CH 2 ) n COOH, wherein n ranges from 1 to 11, c) a sulfomonomer containing an alkali metal sulfonate group on the aromatic moiety of an aromatic dicarboxylic acid and d) at least one aliphatic or cycloaliphatic alkylene glycol having from about 2 to 11, preferably 2 to 8, most preferably 2 to 6 carbon atoms produced.
  • the total acid equivalents present should be substantially equivalent to the total glycol equivalents present on a molar basis.
  • component a) isophthalic acid (component a) to at least about 65 mol% as Acid component to be present.
  • the component a) is preferably pure isophthalic acid, which is present in an amount of about 70 to 95 mol%.
  • any acid with the formula mentioned gives satisfactory results adipic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, Glutaric acid or mixtures of these acids are preferred.
  • the desired amount within the specified range is preferably 1 to 20 mol%, based on the acid components of the copolyester when component b) in the composition is included.
  • the component c) of the preferred copolyester coating Forming monomers should preferably in an amount of at least 5 mol% in be included in this system so that the primer is dispersible with water. Particularly preferably, the amount of monomer of component c) is about 6.5 to 12 mol%.
  • the glycol component d) is in approximately stoichiometric amount present.
  • Acrylic copolymers consist essentially of at least 50 wt .-% of one or several polymerized acrylic and / or methacrylic monomers and 1 to 15 Wt .-% of a copolymerizable comonomer, in the copolymerized state under the action of elevated temperature, optionally without the addition of a separate resinous vehicle for the formation of intermolecular Networking is enabled.
  • the acrylic component of the primer copolymers is preferably in one Amount of 50 to 99 wt .-% present and preferably consists of an ester of Methacrylic acid, in particular an alkyl ester whose alkyl group up to ten carbon atoms contains, such.
  • an alkyl ester whose alkyl group up to ten carbon atoms contains, such.
  • Acrylic copolymers the derived from a lower alkyl acrylate (C1 to C4), in particular ethyl acrylate, give a particularly good adhesion together with a lower alkyl methacrylate between the polyester film and reprographic coatings applied thereto and matte coatings.
  • adhesion promoter copolymers from an alkyl acrylate, e.g. As ethyl acrylate or butyl acrylate, together with an alkyl methacrylate, e.g. As methyl methacrylate, in particular in equal molar Proportions and in a total amount of 70 to 95 wt .-%, used.
  • the acrylate comonomer such acrylic / methacrylic combinations is preferably in a proportion of 15 to 65 mol% present and the methacrylate comonomer preferably in one Proportion, which is generally greater by 5 to 20 mol% than the proportion of acrylate comonomer.
  • the methacrylate is preferably in a proportion of 35 to 85 mol% in the combination included.
  • suitable comonomers are used such. N-methylolacrylamide, N-methylolmethacrylamide and the corresponding ethers; Epoxy materials such. Glycidyl acrylate, Glycidyl methacrylate and allyl glycidyl ether; Containing carboxyl groups Monomers such. Crotonic acid, itaconic acid or acrylic acid; Anhydrides such. B.
  • the preferred acrylate coating can also by the presence of a foreign crosslinking agent such.
  • a melamine or urea-formaldehyde condensation product be achieved. Will not solvent resistance needed, can be dispensed with crosslinking agent.
  • the preferred acrylate coating can be applied to the film on one or both sides become. But it is also possible, only one side of the film with the invention To provide coating and apply to the opposite side another coating.
  • the coating formulation may contain known additives such as. B. Antistatics, wetting agents, surfactants, pH regulators, antioxidants, dyes, pigments, Anti-blocking agents such. As colloidal SiO 2, etc. Usually it is appropriate to a Surfactant to improve the ability of the aqueous coating to wet the Polyester carrier film to increase.
  • the aromatic copolyesters (I-1 and I-2) are made of aromatic dicarboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid or isophthalic acid, optionally branched or fused aliphatic diols such as.
  • aromatic dicarboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid or isophthalic acid, optionally branched or fused aliphatic diols such as.
  • ethylene glycol, Diethylene glycol, 2-methylpropanol or 2,2-dimethylpropanol and a ester-forming compound bearing a water-dispersible functional group produced.
  • the functional groups are: hydroxyl, carboxyl, Sulfonic acid or phosphoric acid groups or their salts. Preferred are Sulfonic acid and carboxylic acid salts.
  • polyvinyl alcohol component (II-1 and II-3) Any polyvinyl alcohol that is water soluble and can be used with normal Polymerization techniques can be produced. Generally, such polyvinyl alcohols produced by the saponification of polyvinyl acetates. The saponification degree should preferably at least 70%, but better 80 to 99.9%.
  • Polyglycerol polyglycidyl ethers (II-2) are reaction products of glycerol and Epichlorohydrin with molecular weights between about 250 and 1200 used.
  • the aqueous polyurethane (I-3) is selected from a polyol such as glycol-terminated polyester, Polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or acrylic polyols, and a diisocyanate such as xylene diisocyanate, Hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, toluidine diisocyanate, Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate, produced.
  • a polyol such as glycol-terminated polyester, Polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or acrylic polyols
  • a diisocyanate such as xylene diisocyanate, Hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diis
  • the intermediate layer consists of the polyesters used for the base layer.
  • the Interlayer may also contain the usual additives described below.
  • the Thickness of the intermediate layer is generally greater than 0.3 ⁇ m and is preferably in the range of 0.5 to 15 microns, especially in the range of 1.0 to 10 microns, especially preferably in the range of 1.0 to 5 microns.
  • the biaxially oriented polyester film according to the invention is the thickness of Cover layer (A) in the range of 1.0 to 7.0 microns, preferably in the range of 1.3 to 6.5 microns and more preferably in the range of 1.6 to 6.0 microns. Is the thickness of the topcoat (A) more than 7.0 microns, the peel force increases significantly and is no longer in the preferred area. In addition, the peel behavior of the film is impaired. On the other hand, if the thickness of the outer layer (A) is less than 0.8 ⁇ m, then the film is in the Usually no longer heat sealable.
  • the thickness of the other, non-sealable cover layer (C) may be the same as the cover layer (A) be different or from this; their thickness is generally between 0.5 and 5 ⁇ m.
  • the total thickness of the polyester film according to the invention can be within wide limits vary. It is preferably 3 to 200 .mu.m, in particular 4 to 150 .mu.m, preferably 5 to 100 microns, wherein the layer (B) has a proportion of preferably 45 to 97% at the total thickness.
  • the base layer and the other layers may additionally contain common additives such as z.
  • additives such as z.
  • stabilizers UV, hydrolysis
  • flame retardants flame retardants
  • fillers she are expediently the polymer or the polymer mixture before melting added.
  • the present invention also provides a process for the preparation of Foil.
  • Cover layer (A) are expediently the respective polymers (polyester I, Polyester II, possibly polyester incompatible polymer [anti-PET polymer] and others Polymers such.
  • the materials can be extruded at about 200 to 280 ° C.
  • Out procedural view (mixing of the various components) has it proved to be particularly favorable when the extrusion of the polymers for the Cover layer (A) performed with a twin-screw extruder with degassing becomes.
  • the polymers for the base layer (B) and for the possible further outer layer (C) and optionally the intermediate layer are useful over others Extruder fed to the (coextrusion) system.
  • the melts are in one Multilayer nozzle formed into flat melt films and stacked on top of each other. Subsequently, the multi-layer film by means of a cooling roller and optionally withdrawn and solidified further rolls.
  • the biaxial stretching of the film is generally carried out sequentially.
  • a simultaneous stretching of the film is also possible, but is not necessary.
  • the sequential stretching is preferably only longitudinal (i.e., in the machine direction) and then in the transverse direction (i.e., perpendicular to the machine direction) stretched.
  • the stretching in the longitudinal direction can be done with the help of two according to the Achieve the desired stretch ratio of different speed rotating rollers.
  • cross stretching one generally uses a corresponding clip frame.
  • the temperature at which the stretching is carried out can be in a relatively large Range vary and depends on the desired properties of the film.
  • the longitudinal direction (machine direction orientation MDO) in a temperature range of about 60 to 130 ° C (heating temperatures 60 to 130 ° C), and transverse direction orientation (TDO) in a temperature range from about 90 ° C (beginning of stretching) to 140 ° C (end of stretching) carried out.
  • the longitudinal stretch ratio is preferably in the range of 2.0: 1 to 5.5: 1, in particular from 2.3: 1 to 5.0: 1.
  • the transverse stretch ratio is preferably in the range from 2.4: 1 to 5.0: 1, especially from 2.6: 1 to 4.5: 1.
  • the preferred temperature range at which biaxial stretching is performed is 60 to 120 ° C during longitudinal stretching (MDO).
  • the heating temperatures of Film in the longitudinal stretching lie in a range of 60 to 115 ° C.
  • the temperatures of the film are preferably in a range from 90 ° C (onset of stretch) to 140 ° C (end of stretch).
  • the longitudinal stretch ratio is in this preferred temperature range in the range of 2.0: 1 to 5.0: 1, preferably from 2.3: 1 to 4.8: 1.
  • the transverse stretch ratio is generally in the range from 2.4: 1 to 5.0: 1, preferably from 2.6: 1 to 4.5: 1.
  • the most preferred temperature range at which the biaxial stretching is performed is, in the longitudinal stretching (MDO) 60 to 110 ° C.
  • the film in the longitudinal stretching lie in a range of 60 to 105 ° C.
  • transverse stretching (TDO) the temperatures of the film are within a range of 90 ° C (beginning of stretching) to 140 ° C (end of stretching).
  • the longitudinal stretch ratio is in this preferred temperature range in the range of 2.0: 1 to 4.8: 1, preferably from 2.3: 1 to 4.6: 1.
  • the transverse stretch ratio is generally in the range from 2.4: 1 to 5.0: 1, preferably from 2.6: 1 to 4.5: 1.
  • topcoat (A) on rolls particularly well bill carried.
  • the non-sealable surface of the Foil according to the known methods are coated in-line.
  • the in-line coating For example, it can lead to improved adhesion between a Metal layer or a printing ink and the film, to improve the antistatic Behavior, processing behavior or even further improvement of barrier properties of the film.
  • the film is over a period of about 0.1 kept at a temperature of preferably 150 to 250 ° C for 10 seconds. Subsequently The film is wound up in the usual way.
  • the gloss of the film surface (B) in the case of a two-layer film or the gloss the film surface (C) in a three-layer film is preferably greater than 100 (measured according to DIN 67530 based on ASTM-D 523-78 and ISO 2813 with Angle of incidence 20 °). In a preferred embodiment, the gloss of this Pages more than 110 and in a particularly preferred embodiment more than 120. These film surfaces are therefore particularly suitable for a further functional Coating, for printing or for metallization.
  • the haze of the film is preferably less than 20%. In a preferred embodiment the haze of the film is less than 16% and in a particularly preferred Embodiment less than 12%.
  • Another advantage of the invention is that the manufacturing cost of Inventive film not significantly above that of a film of standard polyester lie.
  • waste material which is immanent in film production during operation, as Regenerat in an amount of up to about 60 wt .-%, preferably 5 to 50 wt .-%, in each case based on the total weight of the film, again for the film production can be used without affecting the physical properties of the film significantly negatively affected.
  • the film of the invention is suitable for. B. excellent for packaging Foodstuffs, in particular for the packaging of foodstuffs Stimulants in meal trays where peelable polyester foils are used to open the Packaging to be used.
  • Table 1 summarizes the most important preferred film properties again.
  • the determination of the mean diameter d 50 was carried out by means of laser on a Malvern Master Sizer (Malvern Instruments Ltd., UK) by means of laser scanning (other measuring devices are for example Horiba LA 500 or Sympathec Helos, which use the same measuring principle).
  • the samples were placed in a cuvette with water and then placed in the meter.
  • the dispersion is scanned by laser and the particle size distribution is determined from the signal by comparison with a calibration curve.
  • the measuring process is automatic and includes the mathematical determination of the d 50 value.
  • the d 50 value is determined from the (relative) cumulative particle size distribution curve: the point of intersection of the 50% ordinate value with the cumulative curve gives the desired d 50 value (also called median) on the abscissa axis.
  • d 98 and d 10 are again based on the (relative) cumulative curve of the particle size distribution (see above, measurement of the mean diameter d 50 ).
  • the point of intersection of the 98% ordinate value with the cumulative curve immediately gives the desired d 98 value on the abscissa axis and the point of intersection of the 10% ordinate value with the cumulative curve delivers the desired d 10 value on the abscissa axis.
  • the SV value of the polymer was determined by measuring the relative viscosity ( ⁇ rel ) of a 1% solution in dichloroacetic acid in an Ubbelohde's viscometer at 25 ° C.
  • the glass transition temperature T g was determined on the basis of film samples with the aid of DSC (Differential Scanning Calorimetry). A DSC 1090 from Perkin-Elmer was used. The heating rate was 20 K / min and the weight approximately 12 mg. To eliminate the thermal history, the samples were first heated to 300 ° C, held for 5 minutes and then quenched with liquid nitrogen. The thermogram was the temperature for the glass transition Tg was taken as the temperature at half of the step height.
  • a foil strip (100 mm long x 15 mm wide) on the APET side of a corresponding strip of the APET / CPET menu tray and at the set temperature of ⁇ 140 ° C, a sealing time of 0.5 s and a sealing pressure of 4 bar (sealing device HSG / ET from Brugger, DE), both sides heated sealing jaw) sealed.
  • the sealed strips in the tensile testing machine eg., Zwick, DE
  • the 180 ° seal strength d. H. the force required to separate the test strips, with a withdrawal speed of 200 mm / min determined.
  • the seal seam strength becomes in N per 15 mm foil strip (eg 3 N / 15 mm).
  • the sealing device HSG / ET of the company Brugger become as before with the measurement of the Sealing seam strength described, heat-sealed samples (sealed seam 15 mm x 100 mm) produced, wherein the film at different temperatures with the help of two heated sealing jaws at a sealing pressure of 3 bar and a sealing time of 0.5 s is sealed.
  • the 180 ° seal strength was as in the determination of Sealed seam strength measured.
  • the minimum sealing temperature is the temperature at which a seal seam strength of at least 1 N / 15 mm is achieved.
  • the roughness R a of the film was determined according to DIN 4768 at a cut-off of 0.25 mm. It was not measured on a glass plate, but in the ring. In the ring method, the foil is clamped in a ring, so that neither of the two surfaces touches a third surface (eg glass).
  • Wood haze was determined according to ASTM-D 1003-52.
  • the gloss of the film was determined according to DIN 67530.
  • the reflector value was measured as an optical parameter for the surface of a film. Based on the norms ASTM D 523-78 and ISO 2813 set the angle of incidence at 20 °. One Light beam strikes the flat test surface under the set angle of incidence is reflected or scattered by this. The on the photoelectric receiver Striking light rays are displayed as a proportional electrical quantity. Of the The measured value is dimensionless and must be specified with the angle of incidence.
  • the tensile strength of the film was measured according to DIN 53455.
  • the test speed is 1% / min; 23 ° C; 50% r.F.
  • the modulus of elasticity of the film was measured according to DIN 53457.
  • the test speed is 1% / min; 23 ° C; 50% r.F.
  • the polarity of the surface was determined by a contact angle measurement of distilled Water determines. The measurement took place at 23 ° C. and 50% r. F. held. By means of a Dosing syringe is a 1 to 2 mm wide drop of distilled water on the Foil surface applied. Because the measurement is due to heat input of the Lighting (evaporation), charging or spreading behavior is time-dependent, remains the needle in the drop, so that the drop during the measurement carefully enlarged and then immediately by means of a Goniometerokulars the contact angle is read. (Measurement of the progression angle). From 5 measurements becomes the mean educated. (See, for example, ASTM-D 5946-01).
  • Polyethylene terephthalate chips were added to the base layer extruder (B). fed. Also chips of polyethylene terephthalate and particles were the Extruder (twin-screw extruder) for the non-sealable top layer (C) supplied. According to the process conditions listed in the table below The raw materials were melted and homogenized in the two respective extruders.
  • thermoplastic topcoat (A) was a mixture consisting of polyester I and polyester II.
  • the mixture became the Two-screw extruder with degassing for the sealable and peelable top layer (A) supplied. According to the process conditions given in the table below the raw materials were melted in the twin-screw extruder and homogenized.
  • the three melt streams were stacked and ejected via the die lip.
  • the resulting melt film was cooled and then produced via a stepwise orientation in the longitudinal and transverse direction, fixation and subsequent corona treatment (2 kW / m 2 ) of the C-layer, a transparent, three-layer film with ABC structure in a total thickness of 25 microns.
  • the thickness of the cover layer A is 2 ⁇ m, that of the cover layer C is 1 ⁇ m.
  • the minimum sealing temperature of the film compared to the APET side of APET / CPET dishes is 120 ° C.
  • the film was sealed at 140, 160, 180 and 200 ° C against the APET side of APET / CPET trays (sealing pressure 4 bar, sealing time 0.5 s).
  • strips of the composite film according to the invention and the APET / CPET menu shell were pulled apart by means of stress strain testers in accordance with the abovementioned measurement specification (cf., FIG. 2).
  • the measured sealing seam strengths are listed in column 3. Peelable films were obtained for all sealing temperatures.
  • the seal seam strengths compared to APET are in the middle range, ie the films can be pulled off the menu tray without great effort. Furthermore, the film had the required good optical properties, the haze was 5%, the gloss of pages A and C was 120 and 130, respectively. The film had the desired improved adhesion, the contact angle to water was 63.7 °. The film had the desired handling and processing behavior.
  • the film was made as in Example 1, but without corona treatment after biaxial stretching.
  • a 4.5% by weight solids latex consisting of a copolymer of 60% by weight of methyl methacrylate, 35% by weight of ethyl acrylate and 5% by weight of N-methylolacrylamide and a surfactant was prepared according to the following procedure as a primer coating
  • the C-layer of the polyester film was applied: The elongated film was corona treated (8 kW / m 2 ) and then coated by reverse gravure coating on the C layer with the above-described latex.
  • the biaxially stretched film was heat-set at 230 ° C.
  • the dry weight of the coating was about 0.035 g / m 2 at a coating thickness of about 0.0025 ⁇ m.
  • the sealing and peeling properties of the film are as in Example 1.
  • the contact angle to water was 63.8 °.
  • the film was tested for its reprographic adhesion and gave a good adhesion.
  • the film was prepared as in Example 2.
  • An aqueous dispersion having 6% by weight of copolyester consisting of 95% by mole of isophthalate, 5% by mole of Na-5 sulfoisophthalate, and 100% by mole of ethylene glycol, and 0.56% by weight of colloidal SiO 2 became as follows Method applied as a coating on a polyester film:
  • the elongated film was coated by reverse gravure coating on the C layer coated the copolyester dispersion described above.
  • the biaxially stretched film was heat-set at 230 ° C.
  • the dry weight of the coating was about 0.030 g / m 2 at a coating thickness of about 0.0025 ⁇ m.
  • the sealing and peeling properties of the film were as in Example 1.
  • the contact angle to water was 57 °.
  • Two samples of the one-side coated film thus prepared were placed in a vacuum lab coater introduced, in such a way that in one sample, the coated and in the other the uncoated side was metallized.
  • the vacuum chamber was evacuated to below 10 torr, and from a tungsten filament about 500 INGSTROM Aluminum on both the uncoated side and on the coated sample vapor-deposited.
  • each sample was popped up "Metal abrasion" tested.
  • Method abrasion tested on each sample examined was with a Cotton fleece with the same number of strokes and about the same pressure rubbed lightly over the metal surface.
  • the “Abrieb ” of the coated side the film was rated as good.
  • the film was made as in Example 1, but without corona treatment after biaxial stretching.
  • the elongated film was coated by reverse gravure coating with the copolyester dispersion described above.
  • the dry weight of the coating was about 0.040 g / m 2 at a coating thickness of about 0.05 ⁇ m.
  • the sealing and peeling properties of the film were as in Example 1.
  • the contact angle on water was less than 50 °.
  • KX-1 aqueous Polyvinyl acetal solution
  • the coating solution had a concentration of 8% by weight and became applied with a Baker-type applicator with a layer thickness of 127 microns.
  • the coated film was immediately dried at 100 ° C. for 4 minutes placed in an oven.
  • a black square (area: 12 x 12 cm) was with a Ink-jet printer (BJC-600J, Canon Inc.) onto the surface of the dried KX-1 Coating printed and for 12 hours at 23 ° C and 50% relative humidity dried in air.
  • An adhesive tape (cello-tape, Nichiban Inc. width: 18 mm) was glued to the printed area and peeled off quickly. The degree of with the Adhesive tape separated printed surface was determined visually.
  • the coated film showed good adhesion properties.
  • a film as in Example 1 was prepared, but without corona treatment. Of the Contact angle to water was 65.5 ° and the adhesion to metal was poor.
EP20040025893 2003-11-10 2004-11-02 Film thermoscellable et pelable en polyester à adhésivité améliorée, procédé pour sa préparation et son usage Withdrawn EP1529798A1 (fr)

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DE2003152444 DE10352444A1 (de) 2003-11-10 2003-11-10 Haftvermittelte, heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10352444 2003-11-10

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US (1) US7396578B2 (fr)
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EP2062726A1 (fr) * 2007-11-21 2009-05-27 Mitsubishi Polyester Film GmbH Feuille de polyester pour scellement à basse temperature pour des substrates polaires
DE102012106439B4 (de) * 2012-07-17 2014-01-30 Cavonic GmbH Verfahren zum Herstellen eines Kunststoffverpackungsbehälters und Kunststoffverpackungsbehälter
EP3339018A1 (fr) * 2016-12-23 2018-06-27 Mondi AG Emballage avec bandelette d'arrachage
EP3437853A1 (fr) * 2017-07-31 2019-02-06 Mitsubishi Polyester Film GmbH Feuilles en polyester pelables, leur procédé de fabrication et leur utilisation

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CN104354442B (zh) * 2014-10-16 2016-06-01 金宝丽科技（苏州）有限公司 一种防割破型apet复合膜的制备方法
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EP3437853A1 (fr) * 2017-07-31 2019-02-06 Mitsubishi Polyester Film GmbH Feuilles en polyester pelables, leur procédé de fabrication et leur utilisation
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JP2005145068A (ja) 2005-06-09
KR20050045867A (ko) 2005-05-17
DE10352444A1 (de) 2005-06-09
US20050118412A1 (en) 2005-06-02

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